US7625505B2 - Mixtures for evaporation of lithium and lithium dispensers - Google Patents
Mixtures for evaporation of lithium and lithium dispensers Download PDFInfo
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- US7625505B2 US7625505B2 US11/570,816 US57081605A US7625505B2 US 7625505 B2 US7625505 B2 US 7625505B2 US 57081605 A US57081605 A US 57081605A US 7625505 B2 US7625505 B2 US 7625505B2
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- lithium
- evaporation
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 54
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 230000008020 evaporation Effects 0.000 title claims abstract description 31
- 238000001704 evaporation Methods 0.000 title claims abstract description 31
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 15
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims description 20
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 239000000956 alloy Substances 0.000 claims description 19
- 239000008188 pellet Substances 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910007822 Li2ZrO3 Inorganic materials 0.000 claims description 2
- 229910003327 LiNbO3 Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910001069 Ti alloy Inorganic materials 0.000 claims 1
- 229910001093 Zr alloy Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001275 scanning Auger electron spectroscopy Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001883 metal evaporation Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910007786 Li2WO4 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- UKGZHELIUYCPTO-UHFFFAOYSA-N dicesium;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Cs+].[Cs+] UKGZHELIUYCPTO-UHFFFAOYSA-N 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009747 swallowing Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/243—Crucibles for source material
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/30—Doping active layers, e.g. electron transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
- Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
- Y10T428/12063—Nonparticulate metal component
- Y10T428/12104—Particles discontinuous
- Y10T428/12111—Separated by nonmetal matrix or binder [e.g., welding electrode, etc.]
Definitions
- the present invention relates to mixtures to be employed for lithium evaporation in industrial applications requiring the same, as well as to lithium dispensers using these mixtures.
- Lithium has been employed for a long time in the electronics field.
- this metal has been used in the past for the production of photo-sensitive surfaces, such as image intensifiers or photo-multiplying tubes.
- Another important use of lithium, in the form of alloys or salts, is in the formation of battery elements.
- OLED Organic Light Emitting Display
- an OLED is formed of a first planar transparent support (made of glass or plastics); a second support not necessarily transparent, that can be made of glass, metal or plastics, essentially planar and parallel to the first support and fixed along the perimeter thereof, so as to form a closed space; and an active structure in the space for the image formation.
- the active structure is formed of a first series of transparent, linear and mutually parallel electrodes, generally having anodic functionality, being deposited on the first support; a multilayer of different electroluminescent organic materials, deposited on the first series of electrodes and comprising at least one layer of a material conductor of electrons and one layer of a material conductor of electronic vacancies; and a second series of linear and mutually parallel electrodes orthogonally oriented with respect to those of the first series and having cathodic functionality, being in contact with the opposite side of the multilayer of organic materials, so that the latter is comprised between the two series of electrodes.
- lithium As any alkali metal, generally is not industrially employed in the form of pure metal, but rather in the form of compounds that are stable in air at room temperature. Most generally used compounds are the dichromate, Li 2 Cr 2 O 7 , or more commonly the chromate Li 2 CrO 4 , in admixture with a reducing agent. By heating these mixtures at temperatures generally higher than 500° C., a reaction takes place by which chromium is reduced to a lower valence with the consequence of liberating lithium as a vapor. As reducing agents aluminum, silicon or getter alloys, i.e., titanium- or zirconium-based alloys with aluminum or one or more transition elements, are generally used.
- chromates and dichromates of alkali metals have the disadvantage of containing hexavalent chromium, which can cause irritation by contact, swallowing or inhalation and can be carcinogenic in case of long exposures.
- An object of the present invention is to provide mixtures for lithium evaporation, which overcome the problems of the prior art.
- Another object of the present invention is to provide lithium dispensers employing these mixtures.
- lithium salt is chosen among the titanate (Li 2 TiO 3 ), tantalate (LiTaO 3 ), niobate (LiNbO 3 ), tungstate (Li 2 WO 4 ) and zirconate (Li 2 ZrO 3 ).
- FIG. 1 is a perspective, partially cut-away section of a possible lithium dispenser according to the invention
- FIG. 2 is a perspective, partially cut-away section of a preferred embodiment of lithium dispenser according to the invention.
- FIG. 3 is a graph illustrating lithium evaporation properties of dispensers using mixtures of the invention.
- the inventors have found that mixtures of one or more reducing agents with a lithium salt chosen among the above-mentioned ones, not only eliminate the necessity of making recourse to compounds of hexavalent chromium, but also have additional properties that render advantageous their industrial utilization.
- the features (in particular the speed) of lithium evaporation can be easily controlled and reproduced.
- the mentioned lithium salts are much less hygroscopic than the chromium salts, thus reducing the risk that moisture may also evaporate during the lithium evaporation, which is extremely dangerous for the OLED's functioning.
- the preferred one is the titanate, because it is the one showing the highest percentage content of lithium by weight, and also because in the tests carried out by the inventors it has been found that this salt is the one requiring the slightest energy quantity for its evaporation. Besides, it has been observed that lithium titanate gives rise to a particularly smooth lithium evaporation, which is thus easily controllable.
- the reducing agent employed in the mixtures of the invention can be one of the already known components employed in the dispensers based on chromates, such as aluminum, silicon, zirconium or titanium, or alloys containing zirconium or titanium, such as the alloy of percent composition by weight Zr 84%-Al 16%, manufactured and sold by SAES Getters S.p.A.under the mark St 101®, or the alloy having the weight composition Zr 76.5%-Fe 23.5%, manufactured and sold by SAES Getters S.p.A.under the mark St 198®. It is also possible to use a mixture of a plurality of reducing agents.
- both the mixture components generally have particle sizes of less than 1 mm and preferably less than 500 ⁇ m. Still more preferably the particle size is comprised between about 10 and 125 ⁇ m. Powders with particles having a size of less than 10 ⁇ m are generally difficult to be treated in manufacturing and to be kept inside the dispenser. Furthermore, in case of the reducing agent, excessively fine powders can become pyrophoric, giving rise to safety problems in the manufacturing plant. In contrast, with powders with particle sizes greater than those indicated, the contact between the two components of the mixtures becomes worse, and the reaction leading to lithium evaporation slows down.
- the weight ratio between the lithium salt and the reducing agent can vary within wide limits. Preferably, such a ratio is comprised between 10:1 and 1:10.
- the use of the lithium salt in great excess with respect to the reducing agent offers no practical advantage.
- the reducing agent is a getter alloy, such as the cited St 101® alloy, an excess thereof in the mixture can be useful, because the portion not involved in the reaction with the lithium salt can have the effect of sorbing gases, which may be liberated during the reaction.
- a preferred weight ratio between the lithium salt and the reducing agent is 1:5.
- the mixture can be used in the form of loose powders. Preferably, however, it is used in the form of pellets, having the advantage of further improving the contact between the mixture components and facilitating the operations of loading the container.
- Another advantage of pellets as compared to powders, that has been observed by the inventors, is that pellets require a lesser amount of energy for lithium evaporation, and lithium load of the mixture is used more thoroughly, as described in greater detail by a test in the Examples below.
- the container can be made of any material and shape compatible with the application. In particular, as far as the material is concerned, this should be chemically inert against the processing atmosphere and the lithium dispensing mixture at any temperature foreseen in use, which can exceed 1000° C. Furthermore, at the temperatures of use the material forming the container should not undergo substantial physical alterations, such as modifying either its mechanical strength or shape, and must show as low as possible values of gas emission. Materials having these features are, for example, metals or metallic alloys, a few ceramics or graphite. Employing metals and alloys is preferred due to their easier workability and formability. Another advantage in the use of metals and alloys is that the dispenser can be heated to the temperature of lithium evaporation simply by flowing current through the container walls. Preferred metals and alloys for making the container are molybdenum, tantalum, tungsten, nickel, steel and nickel-chromium or nickel-chromium-iron alloys.
- the shape of the container can be any whatsoever among those known from U.S. Pat. Nos. 3,578,834; 3,579,459; 3,598,384; 3,636,302; 3,663,121; 4,233,936; and 6,753,648 B2. Containers of various shapes and materials are also available in the trade, for instance from the Austrian company Plansee or the U.S. company Midwest Tungsten Service.
- a first possible shape of dispenser of the invention is shown in FIG. 1 .
- the dispenser 10 consists of a container with a mixture 14 of the invention inside.
- the container is formed by the assembly of an upper part 11 and a lower part 12 ; the two parts preferably being made of metal and joined to each other, e.g. by spot-welding.
- the lower part shows in its central zone a recess (obtained, e.g., by cold stamping), having housed therein a mixture of the invention, while the upper part has a number of openings 13 , 13 ′, . . . , to allow the emission of lithium vapors.
- the area of part 11 defined by dashed lines corresponds to the recess in part 12 .
- the mixture of the invention can be present in the recess of part 12 in powder form, as shown in the drawing, wherein the mixture is illustrated as element 14 . Alternatively, it is possible to form pellets of the mixture and fill the recess therewith.
- Dispenser 10 has at its two ends “wings” 15 and 15 ′, which are particularly adapted for connection with electrical terminals for heating the dispenser by direct current flow.
- FIG. 2 Another possible shape of dispenser is shown in FIG. 2 .
- This container is the object of, and is described in greater detail in, Italian patent application No. MI2004A002279.
- the dispenser 20 is formed of a central container 21 and a shield 22 .
- Container 21 is closed apart from openings 23 .
- Shield 22 is concentrically arranged around container 21 , and kept in the correct position by spacers 24 (only one shown).
- the shield has openings 25 at positions radially corresponding to openings 23 .
- the mixture of the invention is present with a lithium salt and a reducing agent.
- the mixture is represented in this case as a plurality of pellets 26 , laid in the bottom of the container one next to another. Evaporation of lithium is caused by heating the container, for instance by feeding current to the ends thereof through contacts 27 (only one shown).
- a container like the one shown in FIG. 1 is manufactured by employing sheets of Inconel (an alloy mainly comprising nickel-chromium, plus minor amounts of other metals) having a thickness of 0.2 mm.
- the container has lateral dimensions of 100 ⁇ 24 mm, with a recess 6 mm high being filled up with about 10 g of a mixture of the cited alloy St 101® and Li 2 TiO 3 in a weight ratio of 5:1.
- the mixture is employed in the form of pellets having a diameter of 6 mm and a height of 3 mm, being obtained by compression of the powder mixture under a pressure of about 1700 Kg.
- the dispenser is placed on the bottom of an evacuated chamber, and a small glass plate of lateral dimensions 3 ⁇ 3 cm is placed above the dispenser at a distance of about 20 cm.
- a direct current 100 A over about six hours. The current flow heats the dispenser up to a temperature of about 800° C., thus causing the reaction between the mixture components and lithium evaporation. A fraction of the evaporated lithium condenses on the glass plate forming a thin film thereon.
- the chamber is connected to a sample line of a mass spectrometer (MS) for monitoring the quantities of emitted gases during the evaporation (obviously except for lithium since due to condensation onto the cold walls of the chamber, this element is not sent to the MS measurement). No substantial gas emissions are observed during the whole test.
- MS mass spectrometer
- the quantity of evaporated lithium is estimated by measuring the weight difference of the dispenser before and after the test.
- the weight difference is completely ascribed to the lithium evaporation, thus resulting in a metal evaporation of 100%.
- An analysis of the film formed on the glass plate is also carried out to check its purity, by dissolving it in a HCl solution and chemically analyzing the thus obtained solution through atomic absorption.
- the film contains a quantity of impurities lower than 1% by weight.
- a quartz crystal monitor (QCM), a device well known in the field to measure the growing speed of thin films by exploiting the variation of the quartz crystal vibration frequency as a function of the weight of material deposited thereon. From the knowledge of density and acoustic impedance of metallic lithium, the weight increase is correlated to the increase of film thickness with time, thus obtaining a constant speed of film deposition with a value of about 0.2 ⁇ ngstrom per second ( ⁇ /s).
- a lithium dispenser like the one shown in FIG. 2 is prepared, comprising a cylindrical central container and a shield, both made of stainless steel of 0.2 mm thickness.
- the container is 10 cm long and has a diameter of 3.1 cm, with two holes of 2.5 mm diameter spaced 5 cm apart along a line on its upper part.
- the shield concentrically arranged around the container, is as long as the container and has a diameter of 3.4 cm, with four holes of 11 mm diameter, two holes facing the holes in the container surface, and the other two holes placed between the first two holes and spaced 12 mm apart from each other.
- the container is filled with 110 g of a mixture of the cited alloy St 101® and Li 2 TiO 3 in a weight ratio of 1:1. The mixture is employed in the form of loose powders.
- the dispenser is placed on the bottom of an evacuated chamber and heated by feeding direct current to the ends of the central container, thus causing lithium evaporation.
- the test lasts about 40 hours.
- a QCM is present in the chamber at a distance of 36 cm from the dispenser to measure the speed of growth of a lithium film, which is proportional to the rate of evaporation of the lithium metal from the dispenser.
- the QCM is connected via a feed-back loop to the power source, and the system is regulated to obtain a growth speed of 0.28 ⁇ /s.
- the amount of lithium left in the dispenser decreases, and the temperature required to keep the rate of evaporation increases. This implies a demand for higher power, and thus a higher value of current with time, up to a maximum current value of 300 A (the limit value the system can supply).
- curve 1 represents the trend of film deposition rate (FDR, measured in ⁇ /s, on the left-hand axis of the graph) as a function of the thickness of lithium film deposited (T, measured in ⁇ );
- curve 2 represents the trend of the voltage measured at the ends of the dispenser during the test (Volts, V, right-hand axis of the graph).
- example 2 The test of example 2 is repeated, with the only difference that in this case the lithium dispensing mixture is present in the form of x pellets having a diameter of 6 mm and a height of 3 mm, each one of about 0.3 g in weight, obtained by compression of the mixture of powders under a pressure of about 1700 Kg.
- Curve 3 represents the trend of evaporation rate
- curve 4 represents the trend of the voltage measured at the ends of the dispenser during the test.
- Curve 2 is essentially superimposed to curve 1 all along the test, apart from the end tail where a difference in the behavior of dispensers charged with powders or pellets is observed.
- the mixtures of the invention are suitable for use in industrial processes, as they show constant features of metal evaporation without sudden phenomena, they do not give rise to substantial emissions of potentially harmful gases (such as water), and they allow growth of lithium thin films of high purity in a reproducible way and at a constant speed.
- a comparison of results obtained in Examples 2 and 3 shows that, while both powders and pellets are suitable for the purposes of the dispensers of the invention, dispensers charged with pellets may be preferable as these allow evaporation of lithium for a longer time at a constant evaporation rate (up to a film thickness of about 25800 ⁇ obtained with pellets, curve 2 in FIG. 3 , vs.
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Abstract
Description
Claims (7)
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US12/572,640 US7794630B2 (en) | 2004-09-10 | 2009-10-02 | Lithium dispenser for lithium evaporation |
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ITMI2004A001736 | 2004-09-10 | ||
IT001736A ITMI20041736A1 (en) | 2004-09-10 | 2004-09-10 | MIXTURES FOR LITHIUM EVAPORATION AND LITHIUM DISPENSERS |
PCT/IT2005/000509 WO2006027814A2 (en) | 2004-09-10 | 2005-09-06 | Mixtures for evaporation of lithium and lithium dispensers |
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PCT/IT2005/000509 A-371-Of-International WO2006027814A2 (en) | 2004-09-10 | 2005-09-06 | Mixtures for evaporation of lithium and lithium dispensers |
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US7625505B2 true US7625505B2 (en) | 2009-12-01 |
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US12/572,640 Active US7794630B2 (en) | 2004-09-10 | 2009-10-02 | Lithium dispenser for lithium evaporation |
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US (2) | US7625505B2 (en) |
EP (1) | EP1786946B1 (en) |
JP (1) | JP4804469B2 (en) |
KR (1) | KR101195634B1 (en) |
CN (1) | CN100575536C (en) |
HK (1) | HK1105538A1 (en) |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2015004574A1 (en) | 2013-07-11 | 2015-01-15 | Saes Getters S.P.A. | Improved metal vapour dispenser |
US20160340769A1 (en) * | 2013-07-11 | 2016-11-24 | Saes Getters S.P.A. | Improved metal vapour dispenser |
US9876188B2 (en) | 2013-12-27 | 2018-01-23 | Pioneer Corporation | Light emitting element and method of manufacturing light emitting element |
US20190019646A1 (en) * | 2016-01-08 | 2019-01-17 | Photonis Netherlands B.V. | Image intensifier for night vision device |
US10886095B2 (en) * | 2016-01-08 | 2021-01-05 | Photonis Netherlands B.V. | Image intensifier for night vision device |
Also Published As
Publication number | Publication date |
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TWI388501B (en) | 2013-03-11 |
CN1981066A (en) | 2007-06-13 |
WO2006027814A2 (en) | 2006-03-16 |
EP1786946A2 (en) | 2007-05-23 |
WO2006027814A3 (en) | 2006-05-18 |
JP2008512570A (en) | 2008-04-24 |
CN100575536C (en) | 2009-12-30 |
HK1105538A1 (en) | 2008-02-15 |
US20080042102A1 (en) | 2008-02-21 |
US7794630B2 (en) | 2010-09-14 |
US20100021623A1 (en) | 2010-01-28 |
TW200621638A (en) | 2006-07-01 |
KR20070050920A (en) | 2007-05-16 |
EP1786946B1 (en) | 2014-02-26 |
KR101195634B1 (en) | 2012-10-30 |
ITMI20041736A1 (en) | 2004-12-10 |
JP4804469B2 (en) | 2011-11-02 |
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